Fungicidal sulfonyl-benzotriazole



weather, particularly at elevated temperatures.

FUNGICIDAL SULFONYLBENZOTRIAZO Klaus Sasse and Richard Wegler, Koln-Stammheim, and Ferdinand Grewe, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany N Drawing. Filed Apr. 8, 1958, Ser. No. 727,044 16 Claims. (Cl. 167-33) The present invention relates to and has as its objects fungicidal compositions and a method of combating fungi or protecting plants against fungi attack which comprises treating the plants infested or to be protected with a compound of the following formula SOPR' l 1 wherein R stands for hydrogen, al'kyl, aralkyl, a heterocyclic residue, for OH, OR, SH, SR, O-acyl, S-acyl, H N-NH, N(R) NH-acyl, halogen or N0 and R is a possibly substituted alkyl-, N(R) or OR'-residue, and n is an integer from 1 to 4, or with compositions containing this compound as an active ingredient.

' The protection of plants from attacks by noxious fungi is of great economic importance. However, the number of fungicides which are practically useful for this purpose in spite of great eflforts, is still comparatively small. -Almost all fungicides have partial defects in that they are either not sufticiently plant-compatible at higher concen trations or not sufficiently resistant toweather conditions such as intensive sun irradiation -or prolonged damp Other fungicides are only specifically active thus necessitating a' completion by or combination with further fungicides.

Only a few compounds have so far become known which are sufiiciently active on living plants against fungoid pests such as Phytophthora infestands, Fusicladium (Venturia), Peronospora (Plasmopara), Septoria, Cladosporium fulvum, Alternaria solani, etc., and at the same time cause no damage to the treated plants. Many cornpounds known hitherto show other disadvantages such as strong coloration or unpleasant odor. In conditions of moist warmth these properties are especially noticeable. Other fungicidal substances areunsuitable on account of the too great amount needed for their practical 2,943,017 Patented June 28,- 1960 The symbols in these formulae have the same significance as given above.

A further way of producing these compounds consists in the reaction of an o-phenylene diamine mono-sulfochloride with a compound corresponding to the formula H-R' and finally reacting with nitrous acid:

m N NE I R. I

'Rn SOs-R NHa SOz-R" The symbols in these formulae again have the same sig nificance as given above;

The benzotriazoles substituted by alkyl sulfonyl groups have shown themselves to be especially active as fungicides.

The compounds of the present invention are preferably applied to plants by means of spraying. Spraying of the plants to be treated is preferably performed with aqueous emulsions or suspensions of the active ingredients. Aqueous emulsions or suspensions containing from about 0.01% to about 1% by weight and preferably from about 0.05% to about 0.5% by weight of the active ingredient are practically suitable. If spraying is effected with much smaller quantities of liquid as in low volume spraying higher concentrations of the active ingredients should be employed. If desired a certain amount of a wetting agent can be added to form a suspension of the active ingredient. Any of the conventional wetting agents such as those of anionic, cationic or nonionic type can be employed. Practically suitable, however, are such wetting agents which are of-nonionic type, for instance a polyglycol ether of a benzyl hydroxy diphenyl which may contain from about 12 to 15 glycol radicals. But also other polyethylene glycol ethers of generally alkylated phenols are application, so that shortcomings exist among compounds .1,

of same advantage to bring the compounds of the present inventionin the form ofa suitable'emulsion. Preferably concentrated compositions composing the active' ingredient of the present invention and a suitable wetting agent are prepared at first, sometimes also by means of a suitable trisolvent such as the dimethyl formamide or-acetone. This concentrate then is dispersed in water'just prior to use.

present invention may be applied consists of solutions of the active ingredients in other suitable inert liquid or same solid diluents in which the active ingredient is present preferably in molecularly dispersed form. The form in which the agents to be employed are applied to the object treated depends largely on the nature of the objeot and the purpose of the application.

Suitable 'inert'solvents for the manufacture of liquid preparations should not be readily inflammable, as odorless aspossible and without toxic effects on humans and acid-binding agents, with alkyl-, aryl, or aralkyl-sulfochlop rides, chlorosulfonic acid amides or chloro sulfonic esters.

They are also obtainable from the alkali metal compounds of the benzotn'azoles and the corresponding'sulfochlcirides in inditferent solvents. N.

may of course'also be used.

animals when properly .used. Neither should they have a corrosive efiect on the components of the preparations or the material ofthe storage containers. Examples of such suitable solvents are for instance high-boiling oils such as oils of vegetable origin such as 'castor oil, and lower-boiling solvents. with a flash point of say about '30 C. such as carbon tetrachloride, ethylene dichloride, ethane tetrachloride, hydrated naphthalene, alkylated naphthalene, solvent naphtha etc. Mixtures of solvents The compounds of the. presentinvention can also be applied to plants in the form of dusts, utilizing as the inert vehicle such materials as tricalcium phosphate, precipitated chalk, bentonite, kaolin, kieselghur, and thelike, Al o P w d. pow e and t e l my be Asfurther form in which fungicidal compounds of the used, but in these cases it is advisable 'to add Wetting agents.

The active substances in question may also be used in the form er :aerosols. For-this purpose the active ingredient must be dissolved or dispersed in a solvent boiling belowjroo'm temperature'at atmospheric pressure.

.The invention is illustrated by 'the following examples which are not to be considered as limiting the specification and claims in any manner.

Example 1 possesses, when recrystallized from alcohol, a melting point of 113-114 c. a 7

In an analogous or similar manner the following can be obtained:

l-(dimethylamino sulfonyl) -benzotriazole, M.P.- 8283 C.' (from ligroin) l-(metha'ne sulfonyl)--(or 6)-nitrobenzotriazole, M.P.

. 137138 C. (from alcohol) l( methanesulfonyl)-5-.(or 6-) -chlorobenzotriazole, M.P.

113-1 15 C. (from alcohol) tion with suction. Yield; 16 grams of methane sulfo-(Z- amino-4-methoxy)-anilide, M.P. 14l-152 C.

10.05 grams of methane sulfo-(2-amino-4-methoxy)- anilide are suspended in a mixture of millilitres of glacial acetic acid and 15 mi1lilitres of water. While cooling with ice and stirring there are added below .5 C. 3.5 grams of sodium nitrate in 10 millilitres of water. The temperature is allowed to rise slowly, i.e. to about to C. After 1 hour the suspension'is filtered with suction and the remaining crystals are recrystallized from alcohol. Yield: 8 grams 70.5% of the theoretical of l-methane sulfonyl-S-methoxy-benzotriazole, M.P. 148 149 C. 1"

By the same way can be obtained l-chloromethane sulfonyl-S-methoxy-benzotriazole, M.P. 130--131 C. (from alcohol.) r

' Example 4 In vivo, on the green plants, the inventive compounds have very high fungicidal activity and exceed that for example of zinc ethylene-bis-dithiocarbamate recommended hitherto against Phytophthora infestans on potatoes and tomatoes, as is evident from the following experimental results.

the active ingredient has been mixed with ten times the amount of acetone, whereafter 200%'by weight referred l-chlormethane sulfonyl-benzotriazole, M.P. 9293 C.

(from alcohol) l-methane sulfonyl-S-methyl-benzotriazole, M.P. 1

102 C. (from alcohol) l methane sulfonyl-5-chlor benzotriazole, MP. 1 131 15 C. (from alcohol) l-methane sulfonyl-5fnitro-benzotriazole', M.P. 137-138 .1 C. (from alcohol) l-methane sulfonyl-S-carbethoxy-benzotriazole (from 5- carbethoxy-benzotriazole of M.P. l08-109 C.), M.P. 170 C. (from alcohol). l x l" l-methane sulfonyl-5-carboxy-benzotriazole, M.P. 128 C. (from acetic ester ligroin) Example 2 13.3 grams of S-methyl-behzotriazole are dissolved in a solution of'4 grams of sodium hydroxide in millilitres of water. There are added While stirring dropwise 11.5 grams of methanesulfochl oride in 50 millilitres of acetone. The crystals which precipitate are separated by filtering with suction and recrystallized from alcohol.

Yield: 12 grams=57%' of the theoretical'of l-methanca I a gree of attack atv aconcentration of active agent'of:

sulfonyl-5-methyl-benzotriazole, M.P. 101-102 C.

' V Example 3 I To a solution of 33.6 grams of 4-methoxy-2-nitraniline to active ingredient of benzyl hydroxy diphenyl polyglycol ether containing about between 10 and 15 glycol residues have been added. This premixture ,has been diluted with water to the concentration indicated. in the table below. Twenty-four hours after spraying the plants were artificially infected with Phytophthora-coniaia and incubated in a moist chamber at 18-20 C. Seven days after infection they were evaluated, when theuntreated controls were heavily attacked by the disease. The

' degree of attack of the treatedplants 'was expressed in percent of the attack'of the untreated controls.

EXPERIMENT 1 V Potatoes, Dutch Early/Phytophthora 'infestans. Degree of attack at a concentration of active agents of:

preparation I 0.1% 0.05% 0.025%

zinc ethylene-bisdithiucarbamate 21 43 control 100 in 200 millilitres of pyridine there are added slowly while stirring and cooling 23 grams of methane sulfochloride. The mixture is stirred for half an hour at roointemperature and then 2 hours at 90 C. The solvent is distilled off and the residue is taken up in diluted sodiur'nhyclroxide. This solution is treated once w'ith a small' amount of ether, and then acidified. The crystals' which separate are filtered with suction and'recrystallized from benzene;

Yield: 30 grams of methane sulfo-(2-nitro-4-methoxy) anilide, M.P.-123-124 c; I I a 21.6 grams' of methane sulfo-(2-nitro-4 methoxy)- anilideare suspended'in millilitres of -5%' acetic acid and treated while stirring with small portions'of in toto 35 grams of iron powder. After having added 7 grams of iron-the reaction temperature is adjusted to 90 C. 'After '1' hourreaction at' this temperature, the mixture is made alkaline and filtered with suction. The solution; is neu= tral 'zed arid-the resultingicry'stals are separated byfiltra- EXPERIMENTZ V V Potatoes, Dutch Early/Phyiophthord infstans. De-

preparation 0.1% 0.05%-

l-methane sulfonyl-5-ehlorbenzotriazole- 3 38 zinc-ethylene-bisdithlocarbamate 10 30 control r 100 EXPERIMENT 3 i Tomato plants (Bonny best) of abo'ut6 inches height, planted in pots of about 4 inches diameterin standard soil in the green house, arespread to therun off with suspensions which-have been prepared as shown before. The pots are placed for 24 hours at temperatures to 24 C. in an atmosphere of a humidity of 60 to 70% to allow the spray 'to dry. After that the plants are inoculated with conidia-susp. of Phytophthora i nfestansin aqua bidestilata'and placed in humid chambers .at a temperature ofabout 18? C. the plants are randomized. Humidity in the humid'chanibers is 100% for 48 hours, and is not allowed to be lower than 90% dur-ing the next 4 days. In toto after 6'days after inoculation the results are evaluated. Each pinna of the leaves of the plant has been evaluated by numbers 0 to 4; 0 means no damage, 4 means pinna completely destroyed, 1, 2 and 3 are intermediate values. Each pinna is multiplied with the evaluation number and the total of pinna then is summarized. The number thus obtained is divided through the number of pinna. The control number that means the status of the untreated plants has been set 100, and the status of treated plants has been numbered in percent of the aforementioned control value.

As test material for comparison there has been used zinc ethylene-his-dithiocarbamate. From the results it is to be seen that the inventive compound is far more superior:

Tomatoes (Bonny best), Phytophthora infestans. Degree of attack at a concentration of active agent of:

preparation 0.1% 0.05% 0.025%

N-alkyl-sulfonyl-benzotriazole (mixture of I=C1H| to 04H) 0 13 17 N-chlormethylsulfonyl-benzotriazole- 0 1 7 zinc-athylene-bisdithioearbaruate 1. 7 6 26 control" 100 In addition to the fungi mentioned in the preceding tables, the inventive compound exhibits also activity against Plasmopara viticola (peronospora) on vine, Septoria apii on celery, and Cladosporium fulvum on tomatoes, which is superior to that of standard fungicides such as zinc ethylene-'bis-dithiocarbamate, N-trichloro methylthiotetrahydro phthaJ-imide, tetramethyl-thiuramdisulfide or copper-oxychloride.

EXPERIMENT 4 Tomatoes (Bonny best), Phytophthora infestans. Degree of attack at a concentration of active agent of:

preparation 0.1% 0.05% 0.025%

40 l-methane sulronyl-fi'chlor-benzotriazole 7 42 53 ztue-ethylene-bisdlthiocarbamate 31 54 57 control- 100 EDERIMENT 5 Tomatoes (Bonny best), Phytophthora infestans, degree of attack at a concentration of active agent of:

preparation 0.1% 0.05% 0.025% 1-eh1ormethane sultonyl-B-methoxy-benzotriaznla 7 15 34 zinc-ethylene-hisdithiocarbamate 6 14 control- 6 We claim: 1. A method of combating fungi which comprises treating living plants with a compound of the general formula SOr-R' wherein R stands for a member selected from the group consisting of hydrogen, nitro, chloro, lower alkyl, carboxy-lower alkyl, carboxy, amino and lower alkoxy; R is a member selected from the group consisting of lower alkyl, chloro-lower alkyl and lower alkylamino, and n is an integer from 1 to 4.

. The l-methane-sulfonyl-benzotriazole.

The 1-dimethylamino-sulfonyl-benzotriazole. The l-methane-sulfonyl-S-nitro-benzotriazole. The 1-methane-sulfonyl-6-nitro-benzotriazole. The 1-methane-sulfonyl-5-chlor-benzotriazole. The 1-methane-sulfonyl-6-chlor-benzotriazole. The 1-chlormethane-slflfonyl-benzotriazole. The 1-methane-sulfonyl-5-methyl-benzotriazole.

10. The 1-methane-sulfonyl-S-chlor-benzotriazole.

11. The 1-methane-sulfonyl-S-nitro-benzotriazole.

12. The 1-methane-sulfonyl-S-methoxy-benzotriazole.

13. The 1 methane-sulfonyl-S-carbethoxy-benzotriazole.

14. The l-methane-sulfonyl-S-carboxy-benzotriazole.

15. The 1 chlormethane-sulfonyl-S-methoxy-benzotriazole.

16. A compound of the following formula BOr-R' wherein R stands for a member selected from the group consisting of hydrogen, nitro, chloro, lower alkyl, carboxy-lower alkyl, carboxy amino and lower alkoxy; R is a member selected from the group consisting of lower alkyl, chloro-lower alkyl and lower alkyla'mino, and n is an integer from 1 to 4.

e m es' Chem. Abst., vol. 47, 1953, pp. 11185-86, part 11186 Benson et al.

Chem. Abst., vol. 26, 1932, pp. 114-5. Pollak et al. 

16. A COMPOUND OF THE FOLLOWING FORMULA 